TW409117B - Method for producing phenol and acetone from cumene - Google Patents

Abstract

A process to produce phenol and acetone which comprises concentrating the cumene oxidation products up to the point where a residual cumene content of not less than 21wt% is maintained, decomposing the cumene hydroperoxide with sulfuric acid in a homogeneous phenol-acetone-cumene medium in a mixing reactor while maintaining a phenol-acetone-cumene mole ration of 1:1:(0.38-0.61) and subsequently decomposing the dicumylperoxide formed in a plug flow reactor utilizing a phenol-acetone-cumene mole ration of 1: (1-0.77):(0.35-0.87) at a temperature above 150 DEG C with the addition of a cumene fraction and water. The additional cumene fraction contained in the cleavage product passes downstream through the phenol process and into the cleavage product neutralization step and rectification steps where the cumene fraction is recovered by distillation and partially returned to the dicumylperoxide decomposition step. The increased cumene content of the cleavage product stream gives an improved phase separation in the cleavage neutralization step resulting in less than 20 ppm salt and less than 3.5 wt% dissolved water passing downstream into the rectification steps. The overall steam consumption of the process is reduced 0.4-0.6 ton/ton phenol because of less steam requirements to concentrate oxidation products and to remove water from the neutralized cleavage product at the downstream rectification stages. The process is featured by high selectivity, low cumene consumption of 1302-1305 kg/t phenol as well as decreased hydroxyacetone and mesityl oxide by-product formation.

Description

409117 A7 B7 V. Description of the invention (1) All current methods for the production of phenol and acetone from cumene include the following steps: 1. Cucumene oxide becomes isopropyl bulk hydrogen peroxide (CHP) and by-products include: Toluene (DMBA) and Acetyl Acetate (AP). 2. Preparation by removal of excess cumene (with concentrated CHP)-technical grade CPP and by-products. 3. Acid decomposition (cracking) of technical grade CHP and DMBA by-products including phenol, propane Rhenium and methylstyrene (AMS). 4. Neutralize the acid catalyst contained in the cracked product, and remove the salts formed from the cracked product. 5. Isolate and purify the product through multiple distillation processes The product of phenol researchers is usually easy to focus on improving individual steps instead of developing all the above steps. K through the detailed phenol process to obtain improved reaction selectivity, reduce energy and better operating safety In terms of operational selectivity, recently, much attention has been focused on improving the production of the acidic CHP decomposition step (cracking step), because at this step of the process, a large number of side reactions are formed. Product, especially if it is not properly handled. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) During the acidic cracking technical CHP The DHBA by-products included in the technical grade CHP are particularly troublesome, because t undergoes an odious side reaction in the presence of an acid catalyst to form a repetitive product. The product waste is called " 酴 tar " (which cannot be used > and It represents the loss of valuable original subjects. However, some DMBAs are dehydrated under acidic conditions to form the required AHS. One of the most important criteria for measuring the efficiency of CHP cracking methods is -3- this paper size Applicable to Chinese national standard (CNS > A4 specification (210X297)) 409117 A7 B7 V. Description of the invention (2) The output of the required product AMS derived from DMBA. AMS is needed because it can be manufactured in phenol The downstream step of the method is easily hydrogenated and recovered to become cumene raw material. Then, the cumene can be reused by returning to the pinene oxidation step. Alternatively, AMS can be purified and sold. During the softening of the CHP acid cracking step, the The main methods adopted for AMS production are: 1. chemical method-changing the reaction medium, 2. mechanical method-changing the design of the cracking reactor, 3. a combination of the two above methods. It is shown that the catalytic properties of sulfuric acid as a catalyst in the CHP cracking step can be changed considerably in non-aqueous phenol / propane media because strong hydrogen bonds are formed between phenol molecules and phenol / triose molecules, especially when the phenol / propylene copper is changed At the earing ratio, or when the composition of the reaction medium is changed by adding an inert solvent such as cumene. Water also has a large effect on the activity value of the acid catalyst. Because the phenol-proper-water-cumene in the reaction medium is changed -The combined effect of sulfuric acid ratio on the catalytic properties of the cleaving acid leads to the quantitative effects shown in the following Figures 1, 2 and 3: (Please read the notes on the back before filling this page) Outfitting. Order the Ministry of Economic Affairs The paper standard printed by the Central Bureau of Standards and Shellfish Consumer Cooperatives applies the Chinese national standard (CNS) A4 specification (210X297 mm) 409117 A7 B7 V. Description of the invention (3) K2 = K1 / [H2S04], K2.! / 箅 耳\ S ik 40 'Λ □ τ = 31 ° c 40- 30- 0 30- 20 * D 20- 10- ac 10- 10 20 30 40 K2 X 10, 丨 / Moor X 杪 T = 50eC [pinene] 1st cumene concentration, wtS:: In phenol-acetone medium, the concentration of pinene in Figure 2 can be changed The relationship between the CHP cracking rate constant K2, I0 20. 30 40 50 Acetone concentration, wt! K when the ratio of phenol-propanone is changeable, the dependence of the CHP cracking rate constant K2 (Please read the notes on the back first (Fill in this page again) Κ2..1 / mol X seconds T = 50 C [祜 thin] = 1Q wt% Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

5Q 4ί 30 · 20 ·

10J 1.0 2.0 Ice concentration, y / t% Figure 3: The dependence of the aiHP cracking rate constant K2 when the concentration of water can be changed. These major changes in the CHP cracking rate constant (Figure 3) confirm: In mixed non-aqueous solvents, the phenomenon of acid catalytic activity is greatly changed. It is because of the influence of various components in the cracking medium that the sulfate ion is transformed from strong active acid particles to greatly weakened active acid particles. This difference in acidity function is clear: why the previous technology case reported -5- This paper size is applicable to the Chinese Standard (CNS) A4 specification (210X297 male) 409117 A7 B7 V. Description of the invention (4) Obtained from DHBA AMS varies widely in CHP cracking yield. For example, in the Russian patent case 1361937, when an equal molar concentration of a phenol / acetone mixture was used, the cracked AHS yield was reported to be 40-45X of the theoretical value. In the US patent case 2663735, the acetone which is much larger than the largest < 5: 1 mole of propofol ratio), the AMS yield is 553; Also in Romanian Patent Case No. 63168, when the mol / phenol mixture was replenished with 20 wti cumene, the reported AMS yield was 605S, which is the theoretical value. Also in Romanian patent case 1563181, using 203; excess acetone and only 1-2 w 135 pinene existed, reported AMS yield of 7 0 3! ^ In other prior patents, such as US patents 5257551 and 5530166 , Then obtain the theoretical value of 80 liters of AMS production, in which the cracking medium (up to 20wU cumene and acetone: phenol ratio of 1.5: 1) and the use of a two-reactor system, one is reversely mixed and the other Pseudo-plug flow design. Here, the higher AMS-producing pupae is converted into "part of DMB A by reaction with CHP in the first reactor to dicumyl peroxide (DCP), and then in the second reactor under suitable conditions. It is obtained by decomposing DCP into phenol, acetone, and AMS with high selectivity. Printed by the Central Standards Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperative \\ .. _ _ _ i ^ i. »I---I------ -I i ^^ i. N ------- ^ —J 3.,-卩 · " Please read the notes on the back before filling out this page) In US Patent No. 4,358,618, it is close to the theoretical value of 80SJ The AHS cracking yield was obtained using a three-reactor system using a phenol / acetone medium containing up to 15 wtS: cumene and a mol / acetone medium. Here, the composition of the medium was kept the same across all three reactors (1: 1 : 0.23 phenol-propacumene mole ratio) in a mixed reactor (5 (TC-90 ° C)) and two plug flow reactor (120 ° C -1 5 0 ° C). This paper size applies to Chinese National Standard (CNS) Λ4 specification (2〗 0X297 mm) A7 B7 Printed by Zhongli Biao Junma Employee Consumer Cooperative, Ministry of Economic Affairs Note (5) 1 1 I waited for% research and analysis of the patent information of the first technology shows that the selectivity of the II | CHP cracking step knee * the number of propyl m or cumene in the reaction mixture 1 1 The amount is-" m important factor However, military independence is not enough to produce the most appropriate 1 first 1 AHS output. 0 Reading 1 is more than a discovery. The most important factor is the interaction of all of these factors in conjunction with I. 1 For example, via According to the item gf of the present invention, note 1 matter 1 change the composition to optimize the mol-rzepine-cumene term 1-water molar ratio used in the rain reactor system, and maintain the different molar ratios. In each of the two filled-in I cracking reactor steps, i.e. 5 acidic CHP decomposition step and page 1 I acidic DCP decomposition step 0 1 1 I is the same in all prior, 纛-刖 technology patent cases and in all operating commercial plants. The composition of the 1-dimensional cracking reaction mixture is the same in the hybrid I reactor for CHP decomposition and for plug flow used in DCP decomposition. In the reaction type Dte-reactor, there are 0 more than 1 and 1 is found. In order to obtain the highest AHS selectivity and at the same time * 1 1 is cleaved to m impurities (such as hydroxypropane and a certain base oxide (Example 2- 9)) The formation of t 1 is minimized. The reaction mixture of the reaction mixtures in each backgrinder should be larger than 1 f. The line is different. In the commercial method of making phenol and propionium, not only the reaction selectivity is important. In addition, although the number of microcapsules formed, for example, hydroxypropanyl alcohol (HA) * 1 ί a certain oxygenated oxygen (MO) and dipropanol (DAA) are of great importance »because 1 1 Impurities make downstream purification steps It is complicated and expensive, and it can be used to remove them from the products phenol and propylene. 1 1 Unfortunately, the previous patents for technology ignore the argument of microencapsulation. 1 1 Attention to the sacrifice of the selective AMS step 1 Ⅰ-7 1 1 1 1 This paper size applies to the Chinese National Standard {CNS) A4 specifications (2! 0X297 Gongchu) A7 409117 B7 V. Description of the invention (6) All others thing. As shown by other studies (Table 1), the optimal cleavage conditions for AMS selectivity are not equivalent to the optimal conditions for minimizing the concentration of micro impurities (such as M0). In the rest of the studies (Table 1), a mixture of acetone and phenol-acetone containing cumene was used to reproduce the conditions and temperature ranges reported in the prior art patent US 4358618. Other studies have shown that: When the AMS selectivity is improved by increasing the temperature according to its technology, the amount of M0 formed under the conditions of its cracking method is nasty and increases dramatically (up to 751PPII). This increase in M0 content is from 100ppm: 124ppm to 751ρρβ at 140 * 0. It is extremely noteworthy because the quality of the phenol product purified from the final hydrocarbons issued from the phenol factory must contain less than 15pi > m of M0M to be suitable for sale姶 Most customers. Table 1 No. 〇 Parameter temperature, υ 100 120 140 1 AHS yield, theoretical% < 70 about 73 about 78 2 Μ 0 »ppm 124 3 19 751 In addition, other studies show that: from the previous US technology cases 2663735 and 1109297 M0 content in the cracked product stream of the method (these -S- this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)) ^^ 1 ^^^ 1 1 ^ — ^ — ^^^ 1 ^^ ^ 1 I: J. & ^ 1 In ^^^ 1 ^ J. I ^ -5 (Please read the notes on t before filling out this page) Printed by A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The Ministry of Standards, Bureau of Standards, and Consumers' Cooperative Work. Du printed 5. Invention Description (1) The patent case uses a high excess of acetone.) It even reaches a higher 1 1 value of 1 2 0 0 ρ {] 0. This is extremely possible. Annoying > And cause in the downstream purification steps required to remove H0 from phenols »Incurred extremely high energy use costs 〇 Please 1 I Typical S cumene method for producing phenols uses a considerable amount of steam energy first Read ii 1 1 > It constitutes a high cost. About 7 5% of this energy is consumed. For the purpose of white cracking | 1 to separate and purify propane in the product medium. In step ○, item 1 1 and 1 and m, a very large amount of energy is needed to concentrate the dilute CH P stream produced by the k filled in the cumene gasification step until the intensity required to feed to the CHP cracking step page 1 I step 〇All commercial cumene gasification methods limit the conversion of cumene to CHP. 1 1 degree of chemical conversion to approximately 15 to 35 ¾ * Because above 35% cumene conversion, the selectivity of 9 oxygen 1 I reaction decreases sharply. Normally 9 concentrated CHP% is achieved using a multi-stage steam distillation process to produce a technical grade CHP stream. 9 It contains white 1 to 15 wt% residual pinene. 0 The cumene removed is returned to cumene. Gasification 1 I Step 0 Therefore the forced low cumene conversion required in the S cumene oxidation step results in the use of 1 髙 energy in the subsequent CHP concentration step to produce M technical grade CflP II. For example, 9 in 20 W t% in a single pass in the oxidation reaction m .. The case of I CHP »In order to convert 1.0 ton of cumene > make it completely 1 1 to contain 1-1.5 wt% residual cumene For technical grade CHP, it may be necessary to steam and [1 cycle about 3.87 tons of cumene. This method results in a large amount of 1.2 t ο n / 1 on phenol! A large amount of steam is consumed. 0 During the CHP m reduction step * also Incurred that during the thermal distillation process, some of the thermal decomposition of i CHP became the decomposition products of DM BA and AP. Yu et al. Showed that the number of CH P losses is based on til *. The depth of the shrinkage process. Et al. Research 1 1 Research 9 found: When producing a technique containing 1- 2 w tS P 1 1 * 9-1 1 This paper size applies to Chinese National Standard {CNS) A4 specification (210X 297 mm) u 409117 A7 B7 V. Description of the invention (8) When the amount of DMB A and AP is relatively gasified, The number of founders in the middle school has increased by 20¾. When the CHP, a technique containing 10-15wtSi residual cumene, was produced, the amount of DMBA and AP increased by about 8 to 10¾ compared with those formed at the beginning of this step. In addition, other research heads have shown that when a technical-grade CHP stream is generated, which contains a higher content of residual pinene, up to 25wtSi, the amount of CHP loss due to thermal decomposition decreases during the less stringent distillation process, and The steam energy consumption is correspondingly reduced, approximately 0.95 tons of steam / ton of phenol. t Table 2). (Please read the notes on the back before filling out this page) Printed by the Central Consumer Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, Table 2 In the technical grade CHP, the content of CHP and cumene wt% After the oxidation products are shrunk, DMBA and AP increase * When oxidizing the products of the shrinking reaction, the steam consumes t steam / t phenol CHP cumene 93.0 1.0 20 1.20 83.0 10.0 10 1.12 73.0 25.0 < 0.5 0.95 This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 409117 A7 B7 V. Invention Description (9) Therefore, it is economically advantageous to allow more cumene to remain in the technical grade CHP stream fed to the cracking step. However, none of the previous techniques have been able to take advantage of this situation so far, because it has been found that: the technology containing Trent residual cumene, the homogeneous acidic CHP cracking of the CHP stream may be difficult to control safely. Therefore, previous homogeneous cracking methods used a technical grade CHP stream containing no more than 10-1 2 »t S; residual cumene. The safety argument understood by researchers in the past is that high levels of cumene entering the acidic CHP cracking step will cause reaction inhibition and exothermic reaction (380Kcal / ks) will become uncertain and allow unreacted CHP Accumulates in the cracking reactor, which can cause an explosion. The second argument for which no solution has been found so far is to assume that increasing the amount of cumene in the cracked product will result in a substantial increase, and that the maximum amount of energy required to separate the pinene from the cracked product in the downstream rectification step. However, other studies have shown that this prior art assumption is wrong. Yu et al. ’S calculation of the total energy balance across the entire phenolic process showed that when cracking containing more than 2UU residual cumene technology 鈒 CHP, a lower amount of fiber silicon was used, as opposed to cracking a technology containing l-15vtSi residual cumene 趿 CHP Contrast to the conventional system. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) Two factors contribute to this energy saving. First, energy savings are obtained during the CHP reduction step when a CHP stream is generated containing a technology that exceeds 21wU of residual cumene, as only a small amount of cumene has to be removed. Second, the additional energy is saved in the downstream rectification process, because the higher content of limonene present in the cracked product stream causes less water to become dissolved into the subsequently neutralized cracked product stream, so During rectification " 1 1 paper size applies to Chinese national standard (CNS) A4 size (210X 297 mm) A7 B7 Central Slope Bureau of the Ministry of Economic Affairs®: Industrial and Commercial Cooperative Cooperative Press 5. Invention Description (10 ) 1 1, which requires very little steam and removes water from the purified products of phenol and propane. Water 1 1 The heat required for evaporation (539Kc a 1 / k ε) is more than that required for cumene and organic matter 1 1 (78K ca 1 / ke) is much higher 0 please [first 1 in the case of the present invention »to avoid these disadvantages, to obtain X m choose to read 1 back-1 gain of sexuality * to achieve the required safety and homogeneous CHP cracking stage and No. 1 Increases selectivity »Improves lysis and neutralization steps» Salts Note the process of division. Mystery 1 | Degree 0 and other novel inventions passed the laboratory experiment results shown in Figure 4-7 and Example 2-9 and Table 3 Ψ Item 1.1.1 to PΛ Gu Shi0 Μ Homogeneous acidic decomposition of WCHP in a two-step reactor. Page 1 1 The DCP and DMBAH reactions in the second step should be performed in a reaction mixture having the following I composition. The composition of the reaction mixture used in m is different. • The CHP 1 1T 1 1 cleavage in the first step is carried out. The peptide method allows higher AHS selectivity M and higher DCP selectivity > m cracking reaction performance and minimize the formation of phenol tar 1 t. 1 in the previous, h. U.S. Patent No. 4,358,618 1 using acetol / propene, etc., containing at most 1! 15 V t X cumene Cute Compound * and get its best .. 1 suitable AHS compliance has the white 0.5 ts issued by the second cleavage step. Residual 1 I residual DCP 0 but this residual DCP is lost »because in the downstream process »1 I It is converted to tar» This loss description is equal to 0.55¾ over the total amount of phenol 9 propionate and AMS produced by the 1 1 phenol production process, 1 I However, in the present invention, the use of 1 has: (1 -0.77): (0 · 35-1 1 0. 87) reaction medium with a phenol / propanone / cumene molar ratio of DCP 1 | and DHBA in a second cracking step »this The method comes from AHS selection 1 -1 2-1 1 1 1 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 409117 A7 B7 V. Description of the invention (11) Optional better results and production Only 0.06 to 0.09 * U of residual DCP, resulting in less phenol tar in the end. In the previous cases, it was not possible to obtain a DCP conversion rate close to 100¾. In addition, other studies have shown that at the maximum A MS cracking selectivity, the minimum yield of tartar and the lowest total pinene consumption cannot be obtained (Figure 4). Secret production, theoretical%. Production of aging tar, g / ton, 鼢

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) Figure 4: At different DCP conversion rates MS, the production of AMS and 鼢 tar depends on 1 ton of phenol. Figure 4 shows: based on the selectivity of M AMS alone, comparing various acidic CHP cracking methods is wrong, and rather, cracking industrial technology should be compared. 13- This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ) 409117 A7 B7 V. Description of the invention (12) technology, based on the amount of phenol tar finally formed in this method, or based on the consumption ratio of cumene (ton, cumene / ton, phenol) to Μ Compare. The data of the present invention shown in Figures 5 and 6 shows that the addition of cumene present in the cracked product stream, followed by a softening step in the DCP conversion step, for hydrocarbons from the cracking medium during the subsequent neutralization step. The amount of dissolved water absorbed has a profound effect, in which the catalytic clams in the cracking medium react with the NaOH containing water. Due to the influence of the solubility of the addition cumene, the number of dissolved water in the cracked mass after neutralization decreased from 12 VtX to 3.5 wtS !. As a result, in the cracking and neutralization step, a better phase separation is obtained and the amount of toilet (sodium sulfate) entrained in the separated organic phase is reduced from 2000ppb salts (without the presence of cumene) to 2pp * salts and 40wtS! Cumene is present in the neutralized cracking medium (Figures 5 and 6). The entrained salt is a big problem in the commercial unit because it accumulates in the downstream refining step and contaminates the reboiler of the distillation column, causing expensive repair costs and loss of production. Λί _ II-:: 1 ^ 1--ί ^ —- ·.--I-1 ^ 1-· τ (Please read the notes on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumption The paper size printed by the cooperative is applicable to the Chinese National Standard (CNS) Α4 (210 · 〆297 mm) 409117 Α7 Β7 V. Description of the invention (13 T = 50 ° C [H20] .wl%. [Na2S04l, wl %. j 0.24 0.20 0.16 0.12 0.08 0.04 [cumen] wl% [H20] wt% [Na2S04J wt% 10- 0 15.a 0.1950 -5 ^ 12.0 0.1170 8 · 10 10.2 0.0773 20 7.5 0.0250 6-30 5.C 0.0080 40 3.5 0.0002 4-

T = 40 ° C, 30 20 The solution is based on the amount of stored W in t%, the content of the solution is 4 degrees, the concentration is so concentrated, and the concentration of concentrated ene should be reversed, as shown in Figure 5. Solution concentration% dissolved olefin wt in dry, moderate amount of quality, it is concentrated in the solution of Guanene cracking, and the corresponding amount of stored dry powder is shown in Figure 6 (please read the precautions on the back before filling this page). The results of the present invention list the following advantages for the current phenol processing technology from cumene: 1. The acidic cracking of technical grade CHP containing high content of pinene is safely and efficiently implemented in a homogeneous medium. 2. The acid decomposition of DCP and DMBA into phenol. Propidium and AMS are optimally produced and implemented with paralyzed tar formation that has never been obtained in previous techniques. 3. Reduce the formation of troublesome micro impurities such as oxygenated oxygen and hydroxypropyl hydrazone. 4. Because the cumene concentration is increased, the sodium salt can be more effectively separated from the neutralized cracking medium, resulting in less downstream lithium pollution of the equipment and less frequent repairs: 5. Because of the reduced neutralized cracking medium The water content in the phenol method reduces the energy consumption of the phenolic method (steam > consumption. -15- The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention (14 409117 A7B7 The improved process flow chart of the present invention is shown in Figure 7. The flow is described below. (Please read the notes before the meeting before filling out this page) Install r-, -6. Ministry of Economic Affairs Printed by the Central Bureau of Standards Consumer Cooperatives-16 This paper size applies to China National Standard (CMS) A4 (210 X 297 cm)

409117 A7 B7 Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (16) 1 1 The combined products from the cumene oxidation process flow to the devices 1 A and 1B, where 1 1 1 will be-' part through the distillation process The limonene is evaporated in two or several series-type devices 1 1 and 9 is concentrated and the CHP and gasification by-products are concentrated into the bottom effluent of the column. Please first generate the "technical grade C Η P" liquid stream which contains not less than 21 V t% Residual dry reading 1 olefin t but less than 30 wt. Long. Units 1A and 1B have a standard design 9 under reduced pressure 1 I under 1 »using thin 瞑 evaporator or tray tower with regenerator and Operation 〇Note 1 1 Regardless of the type of evaporator used * Maintain the bottom of the column “Technical Grade C Η P” Item # 1 The cumene leakage in the effluent is preferably 26 ^ 2 8 wt% 〇The obtained technical grade CHP stream has the following composition 1 wt%: Page 1 I CHP '· 75 -64 range; preferably 67- 65 1 I cumene 4 21 -30 range; preferably 2δ- 26 i DMBA t 8- 3 Range 1 Order AP * 1. 2-0. 4 Range 1 DCP: 0. 5- 0. 2 Range 1 1 DMB in technical CHP stream * Concentration of AP and DCP m by-products 1 Degree based on The conditions when operating the upstream pinene oxidation step can be widely changed 9 including 1 1 including cumene conversion depth j temperature and pH value 0 in any case the present invention is not subject to ..) 1 any DMB A t AP or DCP above the number is limited 0 This limit is only related to the concentration of 祜 1 I ene and CH P 阚 1 1 The unit of acidic decomposition (cracking) of technical grade CHP has a conventional design 1 1 (Figure 7) and consists of two or more tubes The shell heat exchanger 2 A t BC is composed of f Water-cooled 〇Technical grade CHP feed and I i ring cracked products pass through the shell 恻 0 CH P cracking system using an acid catalyst maintained at a concentration of 200- 1 1 300p P 1D > via the use of an online conductance Supervisor 1 1-1 8-1 1 1 1 This paper scale is applicable to the Chinese National Standard (CMS) A4 (210X297) 409117 A7 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs B7 5. Invention Description (17) And automation. CHP decomposes in a phenol / acetone medium at a 1: 1 molar ratio (which preferably contains 2 8-2 6 w t S! Cumene, but may contain 2 1-30 0 w t J! A wide range of cumene). The cleavage of technical-grade CHP containing cumene in the above range containing variable numbers is controlled according to the following algorithm: G circ = (4 8 0 · G tchp) / ϋ cumene where: G c ί rc-the cracked product of the cycle Quantity, t / hr Gtchp-quantity of technical grade CHP fed to cracking, t / hr · X cumene-cumene weight present in technical grade CHP X According to the above algorithm, using technical grade CHP raw material 潦Changing the cumene content, implementing an acidic CHP cracking step provides ear characterization and safety and therefore, when using a variable reaction mixture composition (which has a 1: 1: (0.38-0.61) phenol / propane / cumene content) Ratio) to safely control the system. When using the cumene content that can be changed according to the above ratio, the CHP conversion value is still determined and corrected by the δ-T1 value of the on-line calorimeter. The calorimeter is a mini plug-and-roll reactor positioned on the discharge roll from the wheel of the last CHP cracking reactor and is shown on the simplified surface of FIG. 7. This calorimeter monitors the number of unreacted CHPs in the system. If there is a deviation in the CHP conversion, the δ-T1 signal adjusts the cooling water flow rate to the reactors 2A, B, and C to change the reaction temperature M and slow or accelerate the CHP decomposition rate. The interdependence between the algorithm and the calorimeter control meter using S-T1 is improved -19- (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) Α4 size (210 × 297 mm) (%) 409117 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (18) 1 1 Decomposition of the optimal acidic CHP into the desired product 9 Phenol 1 1 AHS and DCP make it annoying The formation of heavy condensed products (such as AHS dimer 1 I and cumyl phenol) is minimized. Please 1 1 Second 1 The cracked product stream containing the least unreacted CHP flows to evaporation. Read 1 1 3 3 Among them, the acetone concentration in the medium t is generated by the heat generated from the decomposition of the CHP on the back of the Ir by using i. The heat generated from the decomposition reaction of the r 1 on the back surface * is evaporated. Result * Matter 1 during DCP and DMBA decomposition steps I Then 1 -1 i Acetone forms less ruthenium oxide and hydroxypropane micro impurities. 0 Acetone distillation :) Reduce the hair and install it adiabatically. F It should be under 400 to 500 nn H g pressure or on the atmosphere page. --- 1 Product at the bottom of white vaporizer 3 at pressure 1 (now little propane) * The cumene fraction of white tower 7 through 1 1 (Scheme IV) (the quantity is 160ke / ton). Technical-grade CHP feed) and circulating water fraction (Process I) from Baita 8 (the quantity is 1- 30.4 kg / t on * Technical 鈒 CHP) meets »and the m-to-1 1 stream flows to DCP and DMBA cracking reactor 4 (it operates like a plug \ 1 J flow reactor) 〇 Keep the CHP concentration in this stream at 0% 〇 So * 1 DCP and DMBA decomposition reaction in the reaction medium P It is optimized while I produces the largest amount of AHS production and it is the same as 1 in the CHP decomposition step m The composition of the medium used is different. As a result of decreasing the acetone concentration and increasing the cumene concentration, the reaction medium fed to the decomposition step of DCP and DMBA is now 1 I with 1: (1-0.77): (0.35 -0.87) 酴 _propyl 鼷 -pinene tfc rate 0-1 I DCP decomposition rate is detected via δ -T2 measured on plug flow vessel 4 to 1 I Μ The DCP and DMBA cracking inverse m efficiency Based on the number of cumene and water accelerated at 151-168 t: 1 I as shown in Example 2-9 〇1 1 I -20- 1 1 1 1 (CNS} A4 specification (2) 0X297 mm) 409117 A7 B7 V. Description of the invention (19) CHP and DCP cracking process control system is maintained by the ratio of δ T2 / 3 T1 0 δ T1 value is in the calorimeter C small reactor) on »the difference between the temperature of the inflow and outflow of the liquid flow and the value of δT2 is the temperature measured across the DCP anti-Pttf reactor Degree difference 0 Keep the tb ratio of δ Τ2 / S Τ1 in the range of 1'.S to 21.4. T should be in the range of 3 to 8. It produces conditions suitable for safe CHP cracking and suitable for DCP selection higher than 97X. Conditions for the conversion efficiency »Not available in other methods 〇 After reactor 4 9 The cracked product is cooled to 30 -50 t! 〇 The cumene m portion from the top of column 7 can be» Although the number is 255ks / to η And water »Its quantity is up to 20kg / t 0 Π» Technical grade CHP is added to the sheltered stream at this location as another method to change the composition of the medium and make it rich in cumene (Process IV b) C & gt The sulfuric acid catalyst is still in the cracked product out of the P container 4. Before starting to refine the main components in the cracking medium, the osmic acid must be neutralized in stage 5 »Neutralize with alkali and neutralize with sulfuric acid. While performing »for example changing sodium hydroxide f carbonic acid And sodium phenol * Attached to the lambda formation of sodium sulphate 0 The sodium osmate forms a condensed bottom aqueous phase in the neutralization stage 5 i decanted it and m opened the bottom of the container 0 more studies have shown: Adding extra cumene to cumene changes the composition of the mixture to effectively and quickly (2 to 3 times faster) the separation of the salts from the neutralized phase. Among other methods, the salt removal efficiency is Above 95¾ and the residual strength content in the organic phase (neutralized cracked product stream) does not exceed 10 to 20 PP WL 〇 By comparison, current industry technology requires the use of large vessels and the use of retention time (1.5 To 24 hours) -21- This paper size applies to China National Standards (CNS) A4 (2I0X297 mm) 409117 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (20) 1 1 Not effectively removed Salt i and even In the presence of lower m cumene, t shifts 1 ί I Desalination has less than 90¾ efficiency 0 The cumene fraction also greatly affects the solubility of water in the top 1 榇 phase and it is continuously cracked during neutralization In the medium »To reduce the dissolution rate, please first dissolve the water to only 3- 3. 5 wt ί 0 See all the results * The current X industry technology also requires the use of a special coalescer device &I; 1 To reduce the amount of salt to the 10 ™ 2 0 ppa content obtained in the present invention > Yu Note matter f etc. can be achieved without purchasing this additional equipment. In the other industrial technologies, item 1 is not required to be expensive The coalescer can obtain the same amount of salt. 0% This equipment is then neutralized with the acid catalyst in vessel 5. First, the neutralized page V, 1 I cracking medium (Scheme VI) is steamed in column 6. The propane (Process VI) 1 1 is removed and the cumene m is divided into two columns 7 and 8; in column 7 1 1 9 the cumene-containing fraction (Process IV) is separated at the top. Here The distillate contains 1 with no more than 1 wt X AMS and 0.3 V t especially age c > at the top of this column t almost all water (Scheme I) is separated from the cumene fraction in a phase separator Separate and feed 1 i to column 8. In column 8 »remove the limonene-AMS fraction from the top 1 l (Scheme IX) and remove the crude phenol bottom 1 1 containing a small amount of cumene and AMS (roller) X) 〇1 Remove all the water (Scheme I) from the top of the white tower 8 and remove the cumene-AMS fraction in the phase separator 1 I, and then recycle it to the conversion reactor 41 to decompose DCP and DMBA. This cycle allows to reduce the amount of fresh water required in this method to about half. 1 As shown in Figure 7 In the process plaque »The total energy consumption is reduced due to the 11 fact: the water solubility of the neutralized cracked product stream was reduced from 10 -12 1 I vt X to 3 to 3, 5 wt X due to the increase The reason for the formation of cumene: 0 1 1 1 -22- 1 i 1 1 This paper size applies Chinese national standards (CNS > A4 specifications (2 丨 OX 297)) A7 B7 Employee Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Printing V. Description of the invention (21) 1 1 Steaming and removing water is a very energy-intensive method. In the remaining inventions 1 1 t this cost is reduced 〇 1 1 Because of CHP concentration steps 1A, B and downstream Distillation column 6 r 7 * 8 Please 1 first 1 The combined saving of the two »The total energy consumption reduction in the whole method is the phenol produced by reading from 1.0 to 0.6 t 〇n / t 〇η Back 1 | 1 The invention and the first a 4 ,. m technology patent case The main characteristics of the difference are as follows. 注意 Note: i 1 1 1 · The CHP during the shrinking phase produces technical grade items containing 21 to 30 residual cumene. The 1 CHP product should contain 26-28 wtS: 〇 Fill out this package 2. Acid decomposition CHP and DCP use different composition of the reaction mixture. Page 1 1 Each g is carried out in a mixing reactor and plug flow reactor 1 while in all previous I 1 technology patent cases 9 the reaction mixture remains unchanged. 1 3. Acid Decomposition of DCP and D Μ Β A is made as f in a plug flow reactor and 1 of them is a) propylene molybdenum in the reaction mixture is reduced due to the pre-removal of the propene and / or the addition of cumene m and water 1 Content and b) use a temperature of 1 1 which allows i DCP and DMBA to produce the most suitable AHS yield together with a minimum amount of 1 I tar formation and has a DCP conversion close to 100¾ less minor impurities! 1 into ≫ I In a comparative prior art, its DCP cleavage reaction mixture uses a white phenol-acetone mole ratio of 11: 1: 1 to 1: 1,5, ie: usually another 1 1 acetone 0 is added but the rest of the invention In the process, no additional propyl m was added to the DCP decomposition II step * and in fact t reduced it and DCP was made by adding pentene m and hydration-\ 1 T instead of using cumene m to make up DCP. And DHB A converted to 1 1 AMS optimization 9 never used in the predecessor technology 0 the combined capacity of the above method 1 I Xu Yu waited to reach the highest selectivity of DCP and 0MB A converted to AHS simultaneously 1 1 -23- 1 1 i 1 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297mm). The consumption of employees of the Central Standards Bureau of the Ministry of Economic Affairs is 409117 'A7 B7. 5. Description of the invention (22) The DCP conversion rate is close to 100X, which is in line with previous techniques. As a result, its DCP conversion rate usually does not exceed 80%. 4. The CHP and DCP cracking process steps are controlled by the ratio ST2 / 5T1 to M, where STT2 is the temperature difference between the inlet and the outlet on the DCP and DHBA reactors, and ST1 is the calorimeter outlet during the CHP decomposition step. The difference from the entrance. This ratio allows to maintain both the required safety and high processing selectivity. 5. Add the added amount of cumene to the cracking and neutralization step to produce improved separation of tritium and reduce hair pollution. The downstream equipment of the rectification stage of the method. 6. The solubility of the water in the neutralized cracked product stream does not exceed 3.5 wt! K (when compared with 6 to 12 vt! S in the prior art), this phenomenon allows to reduce the amount of energy consumed in the process. 7. After the cumene fractions added to the DCP and DMBA cracking stages and to the cracking neutralization stage, the cumene fractions are recycled to the process as a special installed distillation column is used for M separation. 8. It is beneficial to reduce the use of fresh water in the phenol process, as the chemically contaminated wastewater discharged from the process is reduced, which must be treated later in a biological treatment facility. The above-mentioned advantages and characteristics of the present invention are shown in Tables 1 through 9 and summarized in Table 3. Xiao Li 1 f Tu Ling 抻) Manufactures the product of the pinene oxidation step, which has the following composition and has an oxidation selectivity to CHP of 93.17 and 5Ϊ: 1 Applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ( Please read the notes on the back before filling out this page). Packing-Ordering-Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China Yingan 409i: 7 A7 B7 V. Invention Description (23) The names of the constituents of the oxidation products total cumene CHP DMBA AP DCP wt% 71,536 26,7 1.436 0.239 0.089 100 t / hr 147.056 54.887 2.952 0.491 0.183 205.569 Selectivity, Moore S: 93.17 Secondly, the above oxidation product flows to the CHP concentration step, where a portion Parts of unreacted cumene are distilled off and produce a "technical grade CHP" stream having the following composition and it has a CHP selectivity of 92.7 moles, as measured by the oxidation step and the CHP concentration step The selectivity of 0.47 × abs. Loss is generated during the concentration period when the CHP is partially decomposed into DMBA and AP: -25- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 cm) (read Read first (F 'side note, please fill out this page)

4091 ^ 7 A7 B7 V. Description of the invention (2 buckets) Name of the constituents of oxidation products Total cumene CHP DHBA AP DCP Weight! 1; 12.31 81.9 4. 0.8 0.3 100 t / hr 6.1284 41.3514 2.3761 0.4044 0.1517 50.502 Select ， Mole X 92.7; installed --- (please read the precautions on the back before filling this page), 1 printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs during the CHP concentration stage, the steam usage is 0.6 91 ο n / 1 ο n 100¾ C Η P and 1.12ton / ton. The above technical grade CHP liquid stream was fed (50,502 t / hr) to the CHP cracking step, which was in accordance with the prior art of U.S. Patent No. 5,530,166, Example 2 of which was used for the solid reactor, using a reactor group of three flail reactors Mixing reactor. In the presence of 200 to 300 ppm sulfuric acid, the cracked product is circulated in the reaction medium. It is composed of CHP decomposition products and added acetone. The amount of propidium, K, 6025 g per hour according to the required ratio was added to the reaction medium, and CHP was cracked therein. As a result of the addition of acetone to the CHP decomposition reactor, the cracking reaction medium has a molar ratio of phenol: propane: cumene of 1: 1.36: 0.2. -26- This paper size is applicable to China National Standards (CNS) A4 (210 > < 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 409117 A7 ___B7 V. Description of Invention (25) In this way, the product present in the final CHP cracking reactor flows to the CHP cracking reactor operated by the M plug flow vessel. The CHP cracking is carried out using the same compound used in the CHP decomposition step, namely, phenol: triose: cumene in a molar ratio of 1: 1,36: 0.2. The temperature in the DCP cracking reactor was maintained in the range of 90 to 100Ί0. In this example 2 of the prior art patent case, the unconverted DCP present in the reactor was 1.5 wt%. After the DCP cracking step, The additional acetone added to this CHP cracking step was removed in one of the installed evaporators. The removed propane is recycled to the CHP cracking step after condensation. During the evaporation step, in order to reduce the unselected loss of the desired products (tritium and AMS), this previous technique uses a dilute ammonia to introduce it into the evaporator vessel to partially neutralize the catalyst sulfuric acid and prevent Excessive formation of tar. In terms of safety, the CHP cracking step is controlled and K is monitored by maintaining a certain temperature difference between the two calorimeters, which are installed on the outlet stream of the CHP decomposition step and on the way to the DCP cracking reaction. Of the feeder. The amount of major impurities removed in this prior art is shown in the table below, measured after the propionium evaporation step. -27- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (please read the precautions on the back before filling out this page): Packing-.) / -1 .¾-409117 A7 B7 V. Description of the invention (%) Carboxylated base oxyhydroxypropane content PPB 300 1500 By-product AMS AMS Dimer DMBA AP Cuminol DCP content wtX 3.17 0.33 0.34 0.8 0.50 0.24 (Please read the precautions on the back before filling in this Page) 襞. In this prior art, the AHS production after the cracking stage is 76 theoretical, and at the exit of the cracking stage, the production of phenol tar is 44kg / 1 η η. These cracked products are neutralized and separated by adding NaOB to K to separate the resulting sodium sulfate solution, during which the dissolved water content of the neutralized cracking medium is increased to 10-12 wtX. Due to incomplete phase separation, the sodium sulfate content of the cracking medium is 2000 PPB. The neutralized cracking medium containing 10-12 wtX of dissolved water flows to the conventional method, which includes: separation of acetone, a mixture of cumene and AHS, phenol, and high boiling compounds such as tar. The steam used for the separation of acetone from cumene-AMS was 2.9 t / tori phenol. The pinene-to-phenol consumption coefficient was measured at the field after the DCP cracking step and was 1,318 仟 g / t. This paper size is applicable to Chinese National Standard (CNS) A4 (2 i 0 X 297 g t)

II Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 409117 at B7 V. Invention Description (27) The following summary of the method of this prior technical example is provided: required product kg / h ρ age 25470.4 acetone 15869.4 ct-methyl Styrene 1616 by-product at the outlet of the CHP cracking stage kg / t brewing of "phenol tar" 44 steam consumed until distillation to cracking to separate acetone from AMS-cumene t / t phenol 1.12 0.07 2.9 total cumene p-phenol Coefficient, with tar cracking kgA phenol 1313 --------, 'packed-' · '(please read the notes on the back before filling out this page) Order by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Installation Example 2 The product having the composition shown in Example 1 was advanced from the cumene oxidation step, wherein the selectivity obtained was 93.17 moles to the CHP concentration stage. As a result of concentrating the technical grade CHP, it had the following composition: -29 -The size of this paper is applicable to the Chinese standard (CNS) A4 specification (210 × 297 mm) 409117 A7 B7 V. Description of the invention (IV) The names of the constituents of the oxidation products Total cumene CHP DMBA AP DCP weight 30.0 65.68 3.52 0.59 0.21 100 t / hr 18.900 41.3784 2,2176 0,3717 0.1323 63.0 Selectivity, Mohr S: 93.17 This is equal to the selectivity obtained 93. 17 Mohr 3 over all two stages; this confirms: In its concentration stage, there is no unselected CHP decomposition. The steam use in the concentration stage is 0.576t (based on 100JKCHP of Mlt) and 0.933t (based on Klt of Klt). The obtained technical grade CHP (63t / hr) Feed to the cracking stage, which is implemented by K as described in the above process network. The Central Consumers Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives Seal ^^ 1----1-^ 1--^^ 1- ---. * 穴 I-ϋ ——.. 1 ^ 1 U3- ° (Please read the notes on the back before filling this page) The CHP cleavage pseudo is completed in the reaction medium, androgen: Propyl K: The morne ratio of cumene is equal to 1: 1: 0.61. The recycled product is added according to this ratio

Gcirc = (480 * 63) / 30 = 1008m 3 / hr ft can maintain the conversion rate of each batch of CHP. For example, after mixing with the recycled product, the CHP concentration at the reactor inlet is related to the CHP concentration at the reactor population. As measured by the difference in CHP concentration at the exit of the third reactor, (4.3 " " 30 ™ This paper size is applicable to Chinese National Standard (CNS) A4 (2 〖〇 × 297mm) 409117 A7 B7 V. Invention Explanation (29) -0.73) /4.3* 100 = 83.Οχ. The ratio of ΔΤ2 / ΔΤι is 2,3. Due to the change of the cooling water flow rate to the heat exchangers 2A and B t C, the temperature of the CHP cracking process is maintained at 50¾ when the K is maintained at a ΔΤ2 / ATi ratio of 2.3 and Gcirc = 1008n3 / hr. These reaction cracked products are advanced to an evaporator, which contains a mixture of propylammonium, cumene, water and phenol, in an amount of K 44 00 kg / hr, and is distilled under vacuum (340aniHs). The amount M of cumene M 100,000 kg / hr and 1000 kg / hr of water were added to the product flowing out from the lower part of the evaporator 3. As a result of the changes implemented, the reaction medium has the following phenol: propane: pinene ratio of 1: 0.78: 0.8 ?. The concentration of water in each product entering the DMBA and DCP cracking reactor was 2.5 wU. The process of cracking DMBA and DCP was performed at K at 681C. After the DCP and DMB A cracking reactors, the sisters of the main impurities and by-products are shown below: -------- "., Installed-: ---; __ 一定 ----- -, J '(please read the precautions before filling in this page) and fill in this page. The Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China prints impurities and collects oxyhydroxyacetone content PPR 70 950. Byproduct AHS AMS Dimer DHBA AP Dry base age DCP content wtl 2.55 0.13 0.04 0.53 0,19 0.01 -31— This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy 409117 Λ7 B7 V. Invention Explanation (3〇) After 0 (: 1 > -0 ^^ after the cracking stage, the 6113 yield is 90.6! 1 of the theoretical value; the yield of phenol tar is 24.4 kg / t phenol. The obtained cracked product After being neutralized by Na 0 Η, the water content of it was increased to 3.5 wtSi and they were subjected to salt separation. Since the higher pinene content is in the cracked product (the dilute content is 40wU), the dehydration of salts is extremely effective. At the outlet of reactor 5, the degree of maize in the organic phase is 3 ppm. The processed product is separated from the salts (Scheme VI) Proceed to column 6 where the propane distillate is separated on top (Scheme VI). The bottom product of this column proceeds to column 7 where the cumene fraction and water are extracted and separated in a separator. 祜The amount of olefin fraction M10, 00 OU / hr goes to reactor 4 and the water phase (flow Hi) from the separator of column 7 enters column 8 at the amount of Ml, 000 kg / hr, where the cumene-AMS fraction ( Scheme IX) is separated at the top of the column and led to the hydrogenation stage. The difference is that the water phase from the separator (1,000 g / h) is recycled to the DCP-DHBA cracking unit. The acetone and cumene and AMS mixture are separated The steam rate is 2.46 t / t phenol. During the cracking stage, the cumene-to-phenol consumption coefficient is 1 300 kg / t. The following products are produced in this method: This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) (Please read the precautions on the back before filling this page) Pack--9 A7 409117 B7 V. Description of the invention (Η) The required product kg / hr Phenol 25573,6 Propylene 15817,5 α-methyl Ethylene by-product 1794 at the outlet of the CHP cracking stage kg / tSS "Smoke tar" 24.4 Steam consumed To distillation to cracking to separate propane and AMS-cumene t / t brew 0.93 0.08 2.64 Total pinene with tar cracking p-phenol coefficient kg / t phenol 1302 _ (Please read the precautions on the back before filling this page): Installation. Example 3 The method of embodiment 2 in which the composition of the technical grade CHP is I \ The consumer standards of the Central Bureau of Standards of the Ministry of Economic Affairs and Consumer Cooperatives Yinju-33- This paper size applies to Chinese national standards (CNS > A4 specifications (2 丨 〇 X 297 mm) A7 B7 Printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs and printed by the cooperative. V. Invention Description (52) Name of the constituents of the oxidation product CHP DHBA AP DCP Heavy though; 28.00 67.42 3.69 0.62 0.22 100 t / hr 17.1679 41.3686 2.2625 0.3801 0.1349 61.314 Selectivity, Moore X 93.1 This is equal to the selectivity obtained over all two stages t 93.1 Moore X and shows that during its concentration stage, the minimum decomposition of CHP (0.07! tabs. >. The steam used in the concentration stage was 0.58 t (based on MJ's 100JCCHP) and 0.94 t (based on Mlt's phenol). The obtained technical grade CHP (61.314t / hr) was fed to the cracking stage, which was implemented by K as described in the above process network. The CHP cleavage is completed in a reaction medium, in which the ratio of phenol: propane: cumene is maintained to 1: 1: 1,55. Recycling products are added at this ratio

Gcirc = (480 * 61. 31) / 28 = 1 051 πι 3 / hr This ratio can maintain the CHP conversion rate of 76.0% per batch (at AT2 / ATi -34- This paper standard is applicable to Chinese solid standard (CNS) A4 specifications (210X297 mm) --------- {Installation ----- ^ Order ------ (. 4 W ^ (Please read the precautions on the back before filling out this page) 409117 A7 _______B7_, description of the invention (55 '—- when the ratio is 1.5). These reaction cracked products are forwarded to the evaporator, which will contain a mixture of two cumene, water and phenol M 4400kg / hr ». The amount was distilled under vacuum (345 · ηΗβ). The amount of cumene W6,200k / hr and 900 kg / hr of water were added to the product rolled out from the lower part of the evaporator 3. Due to the implementation As a result of the change, the reaction medium has the following 1: 0.78; 〇〇〇〇: two _: cumene ratio into the DMB A and DCP cracking reactor in each product the degree of water salinity is 2.75wt3; DHBA The process of cracking with DCP is carried out at a temperature of 1601. After the DCP and DHBA cracking reactors, the composition of the main impurities and by-products is shown below: (Please read the precautions on the back before filling this page) ------ ^ --- „— ^ Order-- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, a certain substance, a basic oxyhydroxyacetone content PPB 60 920 by-product AMS AMS dimer DKBA AP cumyl phenol DCP content wtX 2.81 0.14 0.05 0.59 0.20 0.02 -35- This paper size applies to the Chinese National Standard (〇 ”5) 8 4 specifications (210 father 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 409117 A7 B7 V. Description of the invention (54) In DCP -After the DMBA cracking stage, the AMS yield is 90.3S of the theoretical value: the yield of aging tar is 25.4ks / t phenol. The cumene fraction is added to the cracked product to obtain a crude concentration of cumene and AMS of 40wtS; The K8790kg / hr @ fi cumene fraction t separated from the top of tower 7 is distributed as follows: 6,200h / h "into the stage of DCP and DMBA cracking and 2,590U / hr to neutralization stage. The separation of salts from the reaction product was performed via Example 2. The amount of salts in the cracked product was 17P0Π1. The vapor rate of the mixture of propane and cumene and AMS was 2.46t / t phenol. During the cracking stage At the time, the consumption coefficient of cumene to phenol was 1301 U / t. The following products were used in this method Produced: -36 ™ This paper scales applicable Chinese National Standard (CNS) Λ4 size (210X297 mm) (Please read the back of the precautions to fill out this page)

409117 A7 __B7 V. Description of the invention () The desired product kg / hr Phenol 25564.5 Acetone 15812.2 Alpha-methylstyrene 1825 By-product kg / t Phenol " Phenol Tar ”25.4 Consumed at the outlet of the CHP cracking stage Steam to distillation to crack to separate acetone and AMS-cumene t / t phenol 0.94 0.08 2.46 Phenene with tar cracking p-phenol coefficient kg / t phenol 1303 (read the precautions on the back before filling this page). Order 1. The method of Example 2 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Example 4, in which the sister of the technical grade CHP is the size of the paper applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 409117 A7 B7 V. Description of the invention (36) The names of the constituents of the oxidation products Total cumene CHP DHBA Α DCP Weight: 21.01 73.94 4.09 0.7 0.26 100 t / hr 11.7522 41.3591 2.2878 0.3916 0.1453 55.936 Selectivity, Morse ------ ^-; 'load-(Please read the precautions on the back before filling out this page) The sore printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs is equal to 逓 and all the options obtained in both stages And 93 mol S; and it shows the non-selective decomposition of CHP (0. 17! «AbS) during its shrinking phase. The steam used for the shrinking phase is 0.63t (based on Klt's 100UHP) and 1.027 t (Based on the phenol of Klt). The obtained technical grade CHP (55.94t / hr) is fed to the cracking stage, which is carried out to K as described in the above process network. The CHP cracking is completed in the reaction medium. , Where the molar ratio of phenol: propane: cumene is maintained equal to 1: 1: 0.38. The recycled product is added according to this ratio

Gcirc = (480 * 55.94) / 21 = 1278m3 / hr This ratio can maintain the CHP conversion rate of 88.0Si per batch (at ΔΤ2 / ΔΤι -38- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 cm) A7 _________B7 _____ 5. The description of the invention (37) is 3. 7 6 o'clock.> These reaction cracked products are forwarded to the evaporator. The mixture containing propanate, dilute, water and phenol is at a rate of 4,400 kg / hr. Although the number is under vacuum (3 0 0 aa H g > steamed 豳. Cumene M 8,500 ke: / hr · amount K and 1, 000 kg / hr of water are added

I into the product flowing out of the lower part of the evaporator 3. As a result of the changes in the gallery, the reaction medium has a phenol: propane: cumene ratio of 1: 0.77: 061. The concentration of water in each product in the DHBA and DC P cracking back-mill was 2.8 wt%. The process of DMBA and DCP cracking was carried out at 151 t. After the DCP and DMBA cracking reactors, the composition of the main impurities and by-products is shown below: tPlease read and read the above precautions and fill in "quote" TV " ° Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Content of Jujube oxyhydroxyacetone content PP 50 50 890 By-product AMS AMS dimer DHBA AP Cu-based age DCP content vtX 2.94 0.16 0.07 0.63 0.24 0.05 -39- This paper is a Chinese standard for rapid use (CNS) A4 Specification (210X297 mm) 409117 Αν B7 V. Description of the invention (58) After 00? -0 »^ six cracking stage, the output of 4 ^ 15 is 88.6 dragons of the theoretical value, and the output of phenol tar is 28.1kg / t phenol . The cumene fraction was added to the cleavage product to obtain a strategic concentration of 40wtai of cumene and AMS. The cumene fraction separated from the top of column 7 in the amount of M14,200 kg / hr was distributed as follows: 8,500 ks / hr entered the stage of DCP and DMBA cracking and 5,700 ks / hr to the neutralization stage. The acid neutralization and the separation of salts from the reaction product were carried out via Example 2. Although the number of salts in the cracked product is 15 ppb, the vapor rate of separating the mixture of acetone and cumene and AMS is 2.55 t / t phenol. At the cracking stage, the cumene-to-phenol consumption coefficient was 1303 kg / t. The following products are produced by the separation of cracked products: (Please read the precautions on the back before filling out this page)-β Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -40- This paper size applies to Chinese national standards ( CNS) A4 specification (210 × 297 mm) AΊ 409117 B7 V. Description of the invention (39) Product required kg / hr Phenol 25548.26 Propylene 15805.8 α-methylbenzyl ethylene 1841 At the outlet of the CHP cracking stage kg / t phenol " phenol tar "28.1 steam consumed to distillation to cracking to separate acetone from AMS-cumene t / t phenol 1.03 0.08 2.55 total cumene plutonium coefficient with tar cracking kg / t phenol 1304 i. ,, Equipment-(Please read the notes on the back before filling this page) '1T- The method printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Example 5 Method 4 where the composition of technical grade CHP is the paper standard applicable to China's national sample Standard (CNS) A4 (210X 297 mm) 7 -1 丄 9 ο 4 B7 V. Description of the invention (4〇) Name of the constituents of the oxidation product CHP DHBA AP DCP Weight X 28.00 67.47 3.69 0.620.22 100 t / hr 17.1679 41.3686 2.2625 0.3801 0.1349 61.314 Selective, Mohr X 93.1, loaded--(Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The technical grade CHP (61.314t / hr) was fed to the cracking stage, which was carried out in the reactor medium (where the ratio of tebufen: propane: cumene to 1: 1: 0.55) was implemented in the reactor. Plutonium products are added at this ratio

Gcirc = (480 * 61.31) / 28 = 1051m3 / hr This ratio can maintain the CHP conversion rate of 76.0¾ per batch (when the ratio of △ Ti / ATi is 2.3). DCP and DMBA of the reaction products in the reactor of the present invention The composition has a molar ratio of phenol: acetone: cumene of 1: 1: 0.53, and the degree of water in the product during the cracking process of DHBA and DCP is 2.81. The DMB A and DC P cracking process is at 156 * C. It will be implemented at the temperature. -4 2-The size of this paper is applicable to Chinese National Standard (CNS) A4 (210X297 mm). Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 409117 A7 B7. 5. Description of the invention (41) After the DMBA cracking reactor, the composition of the main impurities and by-products are shown below: Impurity extraction gasification Hydroxyacetone content PP1 55 910 1 By-product AMS AMS dimer DHBA AP Cucumyl 0CP content tftX 2.85 0.18 0.06 0.61 0.27 0 After 00? -1) 1 ^ 6 cracking stage, the yield of Bing1 (5 is 88.311 of theoretical value, and the yield of tar brewing is 27.7kg / t. The cumene fraction is added to the cracked product to obtain cumene and The rough degree of AMS is 40vt5K. The amount of M10,915kg / hr was separated from the top of tower 7 Pass to the neutralization stage. The acid neutralization and the separation of salts from the reaction products were done via Example 2. The amount of amidines in the cracked product was 18 ppm. Separation of propene and cumene and AMS The used steam rate of the product is 2.46 t / t phenol. During the cracking stage, the consumption of cumene to phenol is 13G2kg.te -4 3-This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) --------}. Act --- -------- .. (Read the notes on r side before filling in this page) 409117 A, A 7 __B7 _ V. Description of the invention ( 42) The following products are produced as a result of separation of cracked products:

MU required product kg / hr phenol 25553.8 propylene 15799 a-methylstyrene 1784.6 by-product kg / t age at the outlet of the CHP cracking stage "phenol tar" 27.7 steam consumed to steaming to cracking to Separation of acetone and AMS-cumene t / t phenol 0.94 0.08 2.46 Phenene with tar cracking p-phenol coefficient kg / t 齢 1304 --------- install-(Please read the precautions on the back before (Fill in this page),-'mouth line example 6 A product with the composition shown below (which is equal to 86.475 £ Morse selectivity) 44 ·-This paper music standard uses China National Standard (CNS) A4 specifications (2 丨 〇 X: 297 mm) 40911Ϋ A7 ΒΊ V. Description of the invention (43) Composition of oxidation products Total names of cumene CHP DHBA AP DCP wt% 72.374 24.2 2.931 0.382 0.113 100 t / hr 152.646 53.346 3.759 0.519 0.152 219.903 Selectivity , Mo Er 3; 86.47) .- ^-(Please read the precautions on the back before filling out this page) Ministry of Economic Affairs, Central Standards Bureau®; Industry and Consumer Cooperatives printed technology from the cumene oxidation stage to the enrichment stage to produce technology Grade CHP ◊ Due to the shrinking technical grade CHP The fruit has the following composition: —45— This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 409117 A7 B7 V. Description of the invention (44) The names of the constituents of the oxidation products total cumene CHP DMBA ΑΡ DCP Weight Dragon 21.00 69,2 8.35 1.12 0.33 100 t / hr 12.1989 40.1983 4.8505 0.6506 0.1917 58.090 Selectivity, mol% 86.3 (Please read the notes on the back before filling this page) Order the staff of the Central Bureau of Standards of the Ministry of Economic Affairs Cooperative printed This is equivalent to the selectivity obtained in all two stages (oxidation and concentration). In the concentration stage, 86.3 moles, the selectivity loss due to the partial decomposition of CHP into DMBA and AP is 0.17i: abs. Technical grade C Η P (5 8. 0 91 / hr) is fed to the cracking stage. If it contains 8. 35 wt S; D Μ BA Technical grade C 的 P cracking M Example 1 (comparative example) The method described in the above is implemented, after the acetone evaporator, the composition of the main impurities and by-products will be as follows: This paper size applies to Chinese national standards (CNS > A4 specification (210 × 297 public epidemic) 409117. A 7 B7 V. Description of the invention (45) Impurities are based on oxygenated hydroxypropylpropion content PPBI 300 1500 byproduct AMS AMS dimer DMBA AP cumyl phenol DCP content wtX 5.72 0.56 0.32 0.89 0.84 0.01 (Please read the precautions on the back first (Fill in this page again) ¥ After the cracking stage, although the AMS yield is 77. 8¾ of the theoretical value, the phenol tar yield is 77.6kg / t phenol during the cracking stage. The steam used to separate the mixture of propane and pinene with AMS was 3.2 t / t phenol. During the cracking stage, the phenol consumption coefficient of cumene is 1350ks / t. The following products are produced by the results of this method:

A Printed by the Central Bureau of Standards, Ministry of Economic Affairs and Consumer Cooperatives—47— This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 409117 A7 _ B7 Five 'invention description (46) The required product kg / hr Phenol 24651.8 Propionate 15351.8 α-Methylstyrene 3336 By-product kg / t phenol "phenol tar" at the outlet of the CHP cracking stage 44 Consumed steam to distillation to cracking to fractionation Propylene and AHS- Cumin t / t phenol 1.12 0.07 3.2 Total cumene p-phenol coefficient with tar cracking kg / t Phenol 1332 (Please read the precautions on the back before filling out this page) / i. Order printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs When the net through the IF96 method is to be cracked with 8.35wtS: DMBA contains the most obtained technical street CHP, the following is obtained: The composition of the reaction CHP cracking medium has 1: 1: 0.42 phenol: propanine: cumen Mole ratio. Recycling products are added according to this ratio

Gcirc = (480 * 58.09) / 2 1 = 1 328 a 3 / hr This ratio can be maintained per batch (^ 1 > Conversion rate is 77.05; (at the time of 1'2 / 8 1'1 = 5.9 at time> gt due to The change of the cooling water flow rate to the heat exchangers 2A, B, and C will be at ΔΤ2 / ATi ratio of 5.9 and Gcirc = 1328n3 / hr a 4 8 _ This paper size applies the Chinese National Standard (CNS) A4 specification {210X297 mm ) 409117 A7 B7 5. In the description of the invention (47), the temperature of the CHP cracking method is maintained at 52t: 1.156 kg / hr of water is added to the product flowing out from the lower part of the evaporator 3. In the DCP and DMBA cracking and In the reactor, the reaction medium has a phenol: propane: pinene ratio of 1: 1: 0.39. The water concentration in the product entering the DHBA and DCP cracking reactor is 3. OwtX. The method of DMBA and DCP cracking is in The temperature was applied to K at 1681. After the DCP and DHBA cracking reactors, the composition of the main impurities and by-products is shown in the following table: Carminyl oxypropylpropane content PP »70 950 by-product AHS AMS dimer DHBA AP cumyl phenol DCP content wtX 6.19 0.53 0.11 1.1 0.79 0.02 Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs- ------ 'Loading--(Please read the notes on the back before filling this page) After the DCP-DMBA cracking stage, the AMS output is 85.4X of the theoretical value and the phenol tar output is 60.4kg / t Add 1 part of cumene energy to the cracked product to get the cumene content in the cracked product is 40 »1 ^. The number of 13,7101 ^ / 111 'will be the most divided from the top of the tower-4 9 _ This paper size applies to China National Standard (CNS) A4 (210X297 cm) 7 1 1 -9.ο 4

7 B V. Description of the invention (48) The separated cumene fraction is added to the neutralization stage. Acid neutralization, the separation of salts from the cleavage products, was carried out via Example 2. The amount of salt in the lysate is 8 ppb. The vapor rate used to separate the mixture of propane and cumene with A MS was 2.δ t / t phenol. At the cracking stage, the cumene-to-phenol consumption coefficient was 1 334 kg / t. As a result of the separation of the cracked products, the following was obtained: (Please read the precautions on the back before filling out this page} The product required for printing by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs kg / hr phenol 24717.8 acetone 15364.6 ct -methylbenzene Ethylene 3665.6 by-product fcg / t at the outlet of the CHP cracking stage " phenol tar " 60.4 steam consumed until distillation to cracking to separate acetone from AMS-cumene t / t phenol 1.03 0.08 2.8 with tar cracking Total cumene p-phenol coefficient kg / t age 1322 -50- This paper size is combined with Chinese National Standard (CNS) A4 (2 丨 0X297 mm) 409117 Λ7 B7 V. Ming (49) The method of Example 3, of which the technical level The composition of CHP is: The name of the composition of the oxidation product. The total weight of the CHP DMBA AP DCP; 1; 21.01 73.94 4.09 0.7 0.26 100 t / hr 11.7522 41.3591 2.2878 0.3916 0.1453 55.936 Selectivity, mole% 93 (Please read first Note on the back, please fill out this page again), -B Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, and feed the obtained technical grade CHP (55.94t / hr) to the cracking stage, which is in the cracking stage. The reactor medium (wherein maintaining phenol: propan-Si: cumene ear which ratio is equal 1: 1: 0.38). I Μ real cell cycle-based product is added in accordance with the ratio

Gcirc = (480 * 55. 94) / 21 = 1 279b3 / hr This ratio can maintain the CHP conversion rate of 88.0S per batch: (when △ Τζ / ΛΤζ = 57). This paper size applies the Chinese national standard (CNS > A4 specification (210 × 297 mm) 409117 A7 _B7__ V. Description of the invention (50) Pass the reaction cracked products to the evaporator, which will contain acetone, cumene f water and The amount of phenol mixture M 4,400 kg / hr · was distilled under vacuum (330 bbHs). 8,500 kg / hr of cumene and 580 kg / hr of water were added to the product from the lower part of the outlet of the evaporator 3. As a result of the changes made, the reaction medium has a phenol: propane: cumene ratio of 1: 0.77: 0.61. The water content in the product entering the DMB A and DCP cracking reactor is 2.1 wtiS. The DCP cracking process is performed at the temperature of M. After the DCP and DMBA cracking reactors, the composition of the main components and by-products are shown in the following table: Impurity: a certain amount of oxypropylpropion content PPB 50 890 by-product AMS AMS dimer DHBA AP cumyl DCP content wtx 2.93 0.20 0.06 0.64 0.29 0.01 Printed by the Consumer Cooperatives of the Central Bureau of the Ministry of Economic Affairs i. Cape ___________.) ^ _Γ__.] I ϊ ~ I. I, Ί (Please (Read the notes on the back before filling out this page)

After the DCP-DMBA cracking stage, the AMS product has a maximum value of 87.6 X -52. This paper size is based on Chinese storehouse standards ((milk) 6 4 grid (210 乂 297 mm) 409117 A7 B7 V. Description of the invention (51), the yield of phenol tar is 28.8ks / t phenol. A cumene fraction containing 40 vtX cumene was added to the cracked product. The limonene fraction (W14, 100kg / hr) separated from the top of column 7 was distributed as follows: 8,500ks / hr was added to the DCP-DMBA cracking stage and 5,600kg / tir to medium And stages. The acid was neutralized and the salts were separated from the cracked product. The salt content in the plutonium cracked product was 16 ppb through Example 2. The steam rate of the mixture of andropropane and cumene and AMS was 2.55 t /. t phenol. In the cracking stage, the cumene-to-phenol consumption coefficient was 1 305 kg / t °. As a result of the separation of the cracked products, the following was obtained: '· 〆l ^ i— 1J ^^^ 1 ^^^ 1— In I--n ^ in (Please read the notes on the back before filling this page)

Printed by the central government of the Ministry of Economic Affairs of the People ’s Consumer Cooperatives * 53 " This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 4〇ηΐ7 '' Α7 Β7 V. Description of the invention (52) Product kg / hr Phenol 25545.5 Propylene 15812.7 Alpha-methylstyrene 1794 By-product kg / t Phenol " Phenol Tar "28.8 at the outlet of the CHP cracking stage Steam consumed until distillation to cracking to fractionation propionate And AMS-cumene t / t phenol 1.03 0.08 2.55 Total pinene p-phenol coefficient with tar cracking kg / 1 IS 1305 (Please read the precautions on the back before filling this page)

、 1T The method of printing example 8 and example 3 from the Central Laboratories of the Ministry of Economic Affairs of Shellfish Consumer Cooperative, where the sister of the technical grade CHP is: This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 409U7 B7 Five Description of the invention (55) The names of the constituents of the oxidation products total cumene CHP DHBA AP DCP weight; K 21.01 73.94 4.09 0.7 0.26 100 t / hr 11.7522 41.3591 2.2878 0.3916 0.1453 55.936 Selectivity, Moore S; 93 m mu ^ 1 ^ 11 m fn In nn In ^^^ 1 \ I,. 0¾-5 (Please read the notes on the back before filling out this page) Employees of the Central Standards Bureau of the Ministry of Economic Affairs, printing products will be obtained by Hezhu Society. CHP (55.94t / hr) was fed to the cracking stage, which was carried out in the reactor medium (wherein, the Mohr ratio of phenol: propane: cumene was maintained equal to 1: 1: 1.38). Adding a few centimeters of the circulating product M 335m3 / hr, it can maintain a ratio of Δ2 / ΔTi of 21.4. The reaction cleavage products such as peptides are passed to an evaporator, and the warm compound M4,40,0 kg / hr containing propylene, cumene, water, and phenol is evaporated under vacuum (330 BitHg). 1,700 kg / hr of water was added to the product exiting from the lower part of the evaporator 3. As a result of the resulting changes, the reaction medium has a ratio of acetone to cumene of 1: 0.77: 0.35. Into DMBA and DCP crack-55- This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm). Central Standards Bureau of the Ministry of Economic Affairs, Monthly Consumer Cooperative, India 409117 ..: A7 B7 V. Description of the invention (54) The water concentration in the product in the decomposition reactor was 4.5 vtS [. The DMBA and DCP cracking process was performed at K at 168D. After the DCP and DMB A cracking reactors, the major impurities and byproducts are shown in the following table: Impurities are based on oxyhydroxyacetone containing eaves f > PB 70 950 byproduct AHS AMS dimer DHBA AP cumylphenol DCP contains 畺 wtiS 3.19 0.21 0.11 0.71 0.31 0.33 After the DCP-DMBA cracking stage, the AMS yield is 83¾. The phenol tar yield is 35.6kg / t phenol. The cumene fraction was added to the cracked product to obtain a 40X cumene content in the cracked product. The cumene fraction (K 1 4, 200 k g / h r) separated from the top of the tower 7 is passed to the neutralization stage. Acid neutralization, the separation of salts from the cleavage products, was carried out via Example 2. The salt content of the cracked product is 18 ppb. The steam used to separate the mixture of acetone, pinene and A MS is 2.55t / -56- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 '乂 297 mm) (Please read the notes on the back before filling This page) Order 409117 a7 B7 V. Description of the invention (55) t phenol. At the cracking stage, the pinene to phenol consumption coefficient is 1 309 kg / t. As a result of the separation of the cracked products, the following were obtained: required product kg / hr phenol 25487.8 acetone 15773.5 ct-methylstyrene 1719.1 by-product kg / t at the outlet of the CHP cracking stage thief "phenol tar" 35,6 Consumed steam to distillation to cracking to separate propane from AHS-cumene t / t phenol 1.03 0.08 2.55 Total cumene p-phenol pseudo-number kg / t with tar cracking 1308 ------; --- -Know-(Please read the notes on the back before filling this page) Order the stamp of the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ Example 9 The method of Example 5, in which the composition of the technical grade CHP is: -57- Applicable to China National Standard (CNS) A4 specification (210X297 mm) 40911? • A7 B7 V. Description of the invention (56) The name of the constituents of the oxidation products want to count cumene CHP DKBA AP DCP weight! 1; 28.08 67.47 3.69 0.62 0.22 100 t / hr 17.1679 41,3686 2.2625 0.3801 0.1349 61.314 Selective, Moore a: 93.1 (Please read the notes on the back before filling in this I ·) ¥! ,, · ΙΒϋί

、 1T Yinfan, the Central Standardization Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, feeds the obtained technical grade CHP (61.314t / hr) to the cracking stage, which is in the reactor medium (where phenol: acetone: cumene is maintained The Mohr ratio is equal to 1: 1: 0,55). Recycling products are added at this ratio

Gcirc = (480 * 6 1 .3 1) / 28 = 1 0 5 1 b 3 / hr This ratio can ensure that the CHP conversion rate of each batch is 76.0S: (when ΔΤζ / ΛΤχ = 3.16). The reaction medium in the DCP-DMBA cracking reactor has a phenol: acetone: cumene ratio of 1: 1.80: 0.51. The concentration of water in the product passed into the DMB A and DCP cracking reactor was 1.3 wtSi. The DHBA and DCP cracking method was performed at 150 ° C. -58- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 409J17 Λ7 _ B7 V. Description of the invention (57) After the DCP and DMBA cracking reactor, the composition of the main impurities and by-products is listed below In the table: Impurity of a certain oxypropyl hydroxypropane content ppm 55 870 By-product AMS AMS Dimer DMBA AP Dimethyl phenol DCP content wU 2.55 0.24 0.02 0.55 0.30 0.01 -Pack-(Please read the precautions on the back first (Fill in this page) Staff Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs

After the cleavage stage of 0 (; bu!) "^ 纟, the yield of six (45 is 85.7 of the theoretical value! |.) The cumene fraction was added to the cracked product to have 40 cumene and AMS content. From the top of column 7 The separated cumene fraction (the amount of M9,4341tg / hr) is passed to the neutralization stage. Acid neutralization, the hydrazone is separated from the cracked product, which is implemented through Example 2. The salts in the cracked product The content is 19 ppm. The steam used for the mixture of tiller acetone and pinene-AMS is 2.46 t / t phenol. During the cracking stage, the phenol consumption coefficient of cumene is 1 306 kg / t. As a result of the cracking product separation, the following was obtained ： -59- This paper size is applicable to Chinese National Standard (CNS) A4g (2ΙΟχ29 ^ 公 itch) ： Employees' Cooperatives Inu 409117 A7 A 7 B7 of the Central Standards Bureau of the Ministry of Economic Affairs 5. Product required for invention (5S) kg / hr phenol 25634.4 triose 12518.5 α-methylstyrene 1752.6 by-product at the outlet of the CHP cracking phase kg / t cool "phenol tar" 30.3 steam consumed until distillation to cracking to tiller acetone and AMS-cumene t / tm 0.94 0.08 2.46 Total cumene with tar cracking Phenol coefficient kg / t | & 1305 -60- (Please read the precautions on the back before filling in this page) Installation · This paper is a fast-moving Chinese national standard (CNS) A4 grid (210X297 mm)

7 B Printed by Niao Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 5. Description of Invention (η) Table 3 Example No. Flow rate, t / hr Loss of selectivity in concentration of CHP% abs * Composition of cracked product, phenol: Mole ratio of propene: cumene Technical grade CHP Gc ire CHP cracking DCP and DMBA cracking 1 2 3 4 5 6 1 50.5 0.47 1: 1.36: 0, 2 1: 1.36: 0.2 2 63 1008 0 1: 1: 0.61 1: 0.78: 0.87 3 61.314 1051 0.07 1: 1: 0.55 1: 0.78: 0,70 4 55.9 1278 0.17 1: 1: 0,38 1: 0,77: 0.61 5 61.34 1051 0.07 1: 1: 0.55 1: 1: 0.53 6 58.09 1328 0.17 1ί1: 0.42 1: 1: 0.39 7 55.9 1278 0.17 1: 1: 0.38 1: 0.77: 0,61 8 55.9 335 0.17 1: 1: 0.38 1: 0.77: 0.35 9 55.94 1051 0.07 1 : 1: 0.55 1: 0.80: 0,51 Example number Temperature during CHP cracking V dT2 / dTl Cumin concentration wtSi Add each component to the CHP and DMBA cracking stage kg / t CHP Technical grade CHP CHP cracking DCP cracking And cumene water 1 7 8 9 10 11 12 13 14 1 100 7.6 12.3 11.46 11.39 11 0 7.1 2 168 2.3 30 30.00 39.89 39.89 159 15.8 3 160 1.5 28 28.00 35 37.52 101 14.67 4 151 3.8 21 21.00 32 37.38 152 17.8 5 156 2.3 28 28.00 27.4 37.66 0 23.7 6 168 5.9 21 21.00 20.58 35.12 0 19.9 7 151 5.7 21 21.00 32 37.45 152 10.3 8 168 21.4 21 21.00 21.15 37.63 0 30.4 9 150 3.16 28 18.00 29 37.49 0 1,03 --61 * (Please read the back first Please pay attention to this page and fill in this page) This paper size is applicable to China National Standards (CNS) A4 specification (2 丨 0'〆297 gong) Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 409117 A7 * 'B7 Wuyi (60) Example number CHP conversion rate% AHS Suspension theory X Production of phenol tar kg / 1 Consumption coefficient of phenol during cracking kg / t Concentration of phenolic substance PP »H0 HA 15 16 17 18 19 20 1 92.5 75.9 44 1318.4 300 1500 2 99,87 90.6 24.4 1300 70 950 3 98.41 90.28 25.4 1301 60 920 4 99.46 88.59 28.1 1303 50 890 5 99.98 88.31 27.7 1302 55 910 6 99,99 85.47 60.4 1334 70 950 7 99.82 87,6 28.8 1305 50 890 8 91.48 84 36 1309 70 950 9 99.71 85.74 30.3 1306 50 870 Example No. 水 Water vapor is used, t / t phenol is added to the neutralization stage kg / t CHP The content of the component after the neutralization is concentrated in the concentrated stage Phase to phase Water consumption wt% Na2S04 PPW cumene 21 22 23 24 25 26 27 1 1.12 2.9 4.02 112 0 12 790 2 0.93 2.46 3.39 11 0 3.5 3 3 0.94 2.46 3.4 9.6 42.4 3.5 20 4 1.03 2,55 3.58 12 102 3.5 15 5 0.94 2.46 3.4 18 178 3.5 18 6 1.03 2.8 3.83 14 236 3.5 8 7 1.03 2,55 3.58 19 100 3.5 16 8 1.03 2.55 3.58 0 254 3.5 18 9 0.94 2.46 3.49 23.81 149 3.5 19 \ / ------ ---: 'Table --- 3 (Please read the notes on the back before filling this page) This paper size is applicable to China National Standards (CNS) Λ4 specifications (210X297 mm). Consumption Cooperative Print Poly 409117 A7 B7 V. Description of the invention (61) Reference symbol description 1 Steam distillation stage (ΙΑ, B) 2 CHP cracking reactor (2A, B, C) 3 evaporator 4 DCP / DMB A cracking reactor 5 Neutralization stage 6 Crude propane tower 7 Cumene fraction separation tower 8 Cumene and AMS separation tower 9 Pipeline for recycling cumene to oxidation stage (Scheme I) 10 Pipeline for feeding cumene oxidation products (Scheme I) 11 Concentrate Oxygenation product line 12 Cooling water line 13 Oxidation product, recycle cracker and catalyst mixer 14 Pump 15 Line for adding catalyst (sulfuric acid) 16 Calorimeter △ T1 Small plug flow reactor 17 Line for removing propane 18 Pipe for supplying cumene / AMS to hydrogenation stage 19 Feeding neutralizer ( NaOH) line 20 Line to the neutralization zone 21 Line from the neutralization stage (Process VI) 22 Wastewater removal line 23 Pump in the neutralization stage -63-

----,-, ---- ^ — (谙 Please read the notes on the back before filling in this page J

J This paper size applies to China National Standards (CNS) Λ4 specifications (21 〇 × 297 mm) A7 B7 V. Description of the invention (θ) 24 Pipeline for crude acetone (process W) 25 Pipeline for crude phenol (process flow) 26 cycles Cumene pipeline (Process IV, IVa, I Vb) 27,27 * Cumene / water separator 28 Line for circulating water (Process I) 29 Phenol / cumene / AMS pipeline 30 Feed phenol / tar to rectification Stage of pipeline (please read the precautions on the back before filling this page) 1 X * \ v ° The standard of the Ministry of Standards and Industry of the Ministry of Industry and Industry f Cooperative Cooperative Prints " 64- This paper size applies to Chinese National Standards (CNS) Λ4 specifications (210X297 public dream)

Claims (1)

Six, apply for a patent ®., Bsl 40911 * 7 a T; V > ^ 88 · 10 · Supplementary Patent No. 87102965 "Method for Producing Phenol and Acetone from Cumin" (Amended in October 88) Patent application scope 1. An improved method for producing phenol and propylene from cumene, in which unreacted cumene is partially removed • The cumene oxidation product is condensed to produce a technical grade CHP stream, which contains 21wt ! i to 30wt! S cumene, preferably containing 2 6 to 2 8 W t. 2. If the improved method of the scope of patent application No. 1 is used, it is used to i-phase homogeneous acid decomposition (cracking) technical grade CHP in a mixed reactor, and acidic decomposition of DCP in a plug flow reactor, where The composition of the cracking medium used for DCP acid decomposition is different from that used for technical grade CHP acid decomposition. 3. The method according to item 2 of the patent application, wherein the molar ratio of phenol: acetone: cumene is maintained at a ratio of 1: 1: (0.38-0.61) of the reaction medium used to crack the technical grade CHP. 4. If you apply for the method of item 2 of the “Lifan”, in which the cracking of technical grade CHP is carried out through the dependence of the concentration of cumene in technical grade CHP as shown below: G cir * c = (4 8 011 G tchp ) / Kuang Sulong Among them: Gcirc is the number of children of the lysate of the cycle, ton / hour (ton / hour Gtchp is the number of CHP technology fed to the lysate step, -1-This paper size applies to Chinese national standards ( CNS) A4 specification (210 X 297 mm) Read the note on the back-note. Re-write the matter, j page I. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs. Printed by the Bayer Consumer Cooperative. 6. Patent application. ®, Bsl 40911 * 7 years Yueyi a T; V > ^ 88 · 10 · Supplementary Patent No. 87102965 "Method for Producing Phenol and Acetone from Cumin" (Amended in October 88) Application of Patent Scope 1. A kind of phenol and propane produced from cumene An improved method, in which unreacted cumene is partially removed. • The cumene oxidation product is condensed to produce a technical grade CHP stream, which contains 21wt! I to 30wt! S cumene, preferably 2 6 To 2 8 W t. 2. As the scope of patent application No. 1 The improved method of item is used for the homogeneous acid decomposition (cracking) of technical grade CHP in a mixed reactor and for the acid decomposition of DCP in a plug flow reactor, wherein a cracking medium for the acid decomposition of DCP is used The composition is different from those used for acidic decomposition of technical grade CHP. 3. For example, the method of the scope of patent application No. 2 wherein the reaction medium composition for cracking technical grade CHP is maintained at 1: 1: (0.38-0.61) phenol: Acetone: Molar ratio of cumene. 4. For the method of applying for the second item of Lifan, in which the technical grade CHP is cracked, the dependence of the cumene concentration in the technical grade CHP is calculated as follows: G cir * c = (4 8 011 G tchp) / Komophosaurus where: Gcirc is the number of cycles of the lysate of the cycle, ton / hour (ton / hour Gtchp is the technology fed to the lysis step, the number of CHP, -1 -This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm). Read the note on the back-Note. Rewrite, j-page I. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs. Printed by the Bayer Consumer Cooperative. A8 B8 C8 D8 409117 VI. Application Patent scope (ton / hour), the heavy child of cumene in the technical grade CHP stream of cumene! K. 5. As the method of applying for the scope of patent item 2, wherein DCP and DM ΒΑ are cracked using a medium (which An ear ratio composition having 1: (1-0.77) :( 0.35-0.87) phenol: acetone: pinene) was implemented in a plug flow reactor. 6. The method according to item 5 of the patent application, wherein the cracking of DCP and DMBA (R) is carried out at a temperature of 151 to 168¾. 7. The method according to item 5 of the patent application, wherein the pinene fraction is introduced into the cracking reactor in an amount of up to 60 kg / ton technical grade CHP so as to decompose DCP and DMBA acidically. 8. The method according to item 5 of the patent application, wherein water is added to the cracking reactor in an amount of 1 to 30.4 kg / to η technical grade CHP to decompose the DCP and DMBA acidically. 9. If the method of item 5 of the profit scope is applied, the DCP conversion rate is higher than 91. 5¾, preferably 98. 5%. 10. The method according to item 2 of the scope of patent application, wherein the method obtains high selectivity and safety by maintaining the value of the temperature difference ratio of ΔΤ2 / ATi in the range of 1.5 to 21.4 (preferably 3-8), In this case, A T2 is the value of the temperature difference between the population and the outlet of the reactor used for the cracking of DCP and DMBA. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Please read the back- Note for re-filling, this page, page I! Order printed by A8, B8, C8, D8, 409117 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs VI. Application for patent scope (ton / hour), cumene $ 僳 Technical grade CHP liquid cumene Heavy child! K. 5. The method according to the scope of patent application, wherein DCP and DM βA are cracked using a medium (which has an ear ratio composition of 1: (1-0.77) :( 0.35-0.87) phenol: acetone: pinene) This is carried out in a plug flow reactor. 6. The method according to item 5 of the patent application, wherein the cracking of DCP and DMBA (R) is carried out at a temperature of 151 to 168¾. 7. The method according to item 5 of the patent application, wherein the pinene fraction is introduced into the cracking reactor in an amount of up to 60 kg / ton technical grade CHP so as to decompose DCP and DMBA acidically. 8. The method according to item 5 of the patent application, wherein water is added to the cracking reactor in an amount of 1 to 30.4 kg / to η technical grade CHP to decompose the DCP and DMBA acidically. 9. If the method of item 5 of the profit scope is applied, the DCP conversion rate is higher than 91. 5¾, preferably 98. 5%. 10. The method according to item 2 of the scope of patent application, wherein the method obtains high selectivity and safety by maintaining the value of the temperature difference ratio of ΔΤ2 / ATi in the range of 1.5 to 21.4 (preferably 3-8), In this case, A T2 is the value of the temperature difference between the population and the outlet of the reactor used for the cracking of DCP and DMBA. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Please read the back- Please fill in the matters needing attention, this page, page I! Order printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed A8 409117 1_ VI. The scope of patent application △ Ti is installed on The temperature difference between the inlet and the outlet of the calorimeter vessel at the outlet of the final reactor of the cracking technology CHP. 11. As in the second method of the patent application, sulfuric acid is used as a catalyst. 12. The method of claim 5 in which the cracking of DCP and DM BA in a plug flow reactor is carried out in a reaction medium with a lower content of acetone; this lower content of acetone is passed through a Items) to c) are realized: a) removing a part of acetone in advance, b) introducing an additional amount of pinene proline and water into the cracked product, c) removing acetone in advance and introducing cumene fraction and water In human lysates. 13. For the method of claim 12 in the scope of patent application, the cumene fraction is separated using a distillation tower to be installed separately. 14. The method as claimed in item 13 of the patent, wherein the separated cumene fraction is added to the cracking reactor of DCP and DM BA and also to the neutralization stage of the cracked products. 15. The method according to item 14 of the patent application, wherein the concentration of cumene and AM S in the cracked product is 40 wtS! When added to the feed of the cracked product neutralization step. 16. The method of claim 2 in which the water content in the cracked product after neutralization is 3.5 wt. -3- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back ®- before filling this page) A Order ---------- line · Ζ Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 409117 1_ VI. Scope of patent application △ Ti is installed at the entrance and exit of the calorimeter container on the exit of the last reactor used in the cracking technology-grade CHP The temperature difference value. 11. As in the second method of the patent application, sulfuric acid is used as a catalyst. 12. The method of claim 5 in which the cracking of DCP and DM BA in a plug flow reactor is carried out in a reaction medium with a lower content of acetone; this lower content of acetone is passed through a Items) to c) are realized: a) removing a part of acetone in advance, b) introducing an additional amount of pinene proline and water into the cracked product, c) removing acetone in advance and introducing cumene fraction and water In human lysates. 13. For the method of claim 12 in the scope of patent application, the cumene fraction is separated using a distillation tower to be installed separately. 14. The method as claimed in item 13 of the patent, wherein the separated cumene fraction is added to the cracking reactor of DCP and DM BA and also to the neutralization stage of the cracked products. 15. The method according to item 14 of the patent application, wherein the concentration of cumene and AM S in the cracked product is 40 wtS! When added to the feed of the cracked product neutralization step. 16. The method of claim 2 in which the water content in the cracked product after neutralization is 3.5 wt. -3- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back ®- before filling this page) A Order ---------- line · Ζ A8 A8 C8 D8 409117 B8 VI. Application for patent scope 17. For the method of the second scope of patent application, after the neutralization stage of the cracking product, the salt (sodium sulfate) content is 3 to 20 PP. 18. For example, the method of claim 2 of the patent scope, in which the energy consumption of the entire method is reduced due to the following factors a) to c): a) the higher content of cumene in the technical grade CHP stream b) The cumene fraction is introduced into the cracked product. C) The neutralized cracked product has a lower solubility in water. 19. The method according to item 5 of the patent application, wherein the amount of formed base gas is reduced to 50-70 ppm and the amount of hydroxyacetone formed is 870 to 950 PP. Please read the "Notes on the back" before filling in this page. I Itt Line Λ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) A8 A8 C8 D8 409117 B8 VI. Application scope of patent 17. The method of the scope of patent application No. 2 wherein the content of salts (sodium sulfate) after the neutralization stage of the cracking product is 3 to 20 PP. 18. For example, the method of claim 2 of the patent scope, in which the energy consumption of the entire method is reduced due to the following factors a) to c): a) the higher content of cumene in the technical grade CHP stream b) The cumene fraction is introduced into the cracked product. C) The neutralized cracked product has a lower solubility in water. 19. The method according to item 5 of the patent application, wherein the amount of formed base gas is reduced to 50-70 ppm and the amount of hydroxyacetone formed is 870 to 950 PP. Please read the ‘Notes and Items on the back’ before writing this page. I Itt Line Λ Printed by the Consumers ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm)